Fungicidal use of a 1,2,4-triazole nickel salt complex

ABSTRACT

Fungicidal compositions and their use in the control of phytopathogenic fungi which contain as the active ingredient compounds belonging to the class of metal salt complexes of 4substituted-1,2,4-triazoles.

United States Patent [191 Bayer et al.

[ F UNGICIDAL USE OF A 1,2,4-TRIAZOLE NICKEL SALT COMPLEX [75] Inventors: Horst O. Bayer, Levittown; Richard S. Cook, Doylestown; William C. Von Meyer, Willow Grove, all of Pa.

Related US. Application Data [62] Division of Ser. No. 847,482, July 3, 1969, Pat. No. 3,647,810.

[52] US. Cl. 424/245 [51] Int. Cl A0ln 9/22 [ll] 3,821,376 [4 June 28, 1974 [58] Field of Search 424/245 [56] References Cited UNITED STATES PATENTS 1,580,572 4/ i926 Rathsbiirg 260/299 3,647,810 3/1972 Bayer et al.. 260/299 Primary Examiner-Albert T. Meyers Assistant Examiner-Le0nard Schenkman [571 ABSTRACT Fungicidal compositionsand their use in the control of phytopathogenic fungi which contain as the active ingredient compounds belonging to the class of metal salt complexes of 4-substituted-1,2,4-triazoles.

2 Claims, No Drawings FUNGICIDAL USE OF A 1,2,4-TRIAZOLE NICKEL SALT COMPLEX This is a divisional of US. application Ser. No.

847,482, filed July 3, 1969 now Pat. No. 5

This invention is concerned with fungicidal compositions and their use which contain as the active ingredient compounds belonging to the class of 4-substituted- 1,2,4-triazole-metal salt complexes. These novel compounds may be represented by the formula oxy or the NR'R group wherein R and R are hydrogen or lower alkyl, and a phenoxy or thiophenoxy group which may be substituted in the aryl group with lower alkyl, lower alkoxy, halo preferably chloro, or

nitro groups; alkenyl of 2 to 6 carbon atoms; alkynyl of 30 2 to 6 carbon atoms; cycloalkyl of 3 to 8 carbon atoms; aralkyl of up to 10 carbon atoms; aralkyl of up to 10 carbon atoms substituted in the aryl group with lower alkyl, lower alkoxy, halo preferably chloro, and nitro groups; aryl; lower alkyl, lower alkoxy, halo preferably chloro and nitro substituted aryl; and heterocyclic groups, preferably selected from the group consisting of 2-pyridyl, 3-pyridyl; 4-pyridyl, 3-(l,2,4-triazyl), 4- (l,2,4-triazyl), 2-pyrimidyl, 2-thiazyl, 2-benzothiazyl and its chlorinated derivatives;

M is a metal cation, such as cadmium, cobaltous, cupric, ferrous, ferric, manganous, mercuric, nickel, silver, stannous and zinc, with a transition metal cation such as cupic, ferrous, manganous, mercuric and zinc and complexes of the transition metal cation, such as complexes with ammonia or amines, being preferred;

X is an anion forming a compound with the cation M, the said compound having sufficient-solubility to form the complexes of the invention, or a dithiocarbamate, preferably an alkylenebisdithiocarbamate such as ethylenebisdithiocarbamate or propylenebisdithiocar-- bamate, or an N-mono(lower-alkyl)dithiocarbamate or an N,N-di(lower-alkyl)dithiocarbamate;

a is the integer 1 when M is mercuric or silver or when X is a1kylenebisdithiocarbmate and is the integer 2 for all other definitions of M and X;

n is an integer which for the anion X satisfies the va-' lence of the metal ion M. The term lower as used above refers to a carbon content of l to 6 carbon atoms. The selection of X is not critical, but for economic reasons preferred anions are acetate, a dithiocarbmate, a halide preferably chloride, nitrate and sulfate. The values of M, X, a and n and accordinglythe structures of the metal salt complexes are influenced by the nature of the anions.

1,2,4-Triazoles are known to be amphoteric in nature, forming salts with acids and with bases (see K. T.

Potts, Chemical Reviews 61, 112 (1961). While 3- amino- 1 ,2,4-triazo1e is known to form precipitates with ferric and cupric ions (see Menoret and Tracez, Compt. rend. 244, 2827 (1957)), there are no literature references to a metal salt complex of a 4-substituted-l,2,4-triazole.

The novel compounds of this invention are prepared by reacting a solution of a 4-substituted-l,2,4-triazole with a solution of a metal salt of the formula MX for those cases where X is other than a dithiocarbmate. The following equation depicts this wherein the symbols R, M, X, a and n have the meanings given above. It is preferred that the moles of reagents used correspond to the stoichiometry which appear in the isolated product; however, an excess of the triazole may be used. Te complexing of the two reagents proceeds readily at room temperature although any temperature in the range of 0-l00 C. may be used. The solvent is not critical and may be any one in which the two reactants are soluble. Preferred solvents are polar ones such as water and alcohols, such as methanol methanol. The resulting 4-substitute d-l ,2,4

triazole-metal salt complex may precipitate or may remain in solution. When the product is an insoluble solid it may be isolated by filtration; otherwise, the product may be isolated by removal of the solvent.

For the case where X is a diithiocarbamate the method of preparation involves reaction of a mixture of the 4-substituted-l,2,4-triazole and a soluble dithiocarbamate salt with a solution of the metal salt MX, where X is other than dithiocarbamate. Typical dithiocarbamate salts which may be used include sodium, potassium, calcium and ammonium. An excess of the dithiocarbamate is to be avoided since this would result in the concurrent formation of some metallic dithiocarbamate. An excess of the 1,2,4-triazole may be used. The reaction conditions for this are the same as given above for MX salts in general. Water is the preferred solvent. The following equation using sodium ethylenebisdithiocarbamate as the dithiocarbamate reactant and where n is 2 depicts a typical reaction -alkoxymethylene- N-formylhydra2ine which is then reacted with a pril 0H ROH H1O ,4-triazoles may be Analytical data A Percent: H Percent N Percent C 1368 (1953) which involves the reaction of RNH wherein R has the meaning given above. The following reaction depicts this:

ROCH=NNHCHO RNHZ -substituted-l ,2

in a solvent such as benzene and is catalyzed by acids such as p-toluenesulfonic acid. They may also be made by the method of Wiley and Hart as described in J. Org. Chem., 18,

erocyclic primary amine.

The intermediate compounds of Formula ll may also be made by reaction of an orthoformate, (R'O) CH, with formylhydrazine to give an N mary amine 2 l5 (ROhCH NHQNHCHO 20 who... The resulting 4 used as the crude product isolated as a residue from the 25 reaction mixture or may be purified by standard means, (H) such as distillation. The following Table I lists typical 4-substituted- 1 ,2,4-

triazoles useful as intermediates in the preparation of the metal salt complexes.

TABLE 1 4-substituted-1,2,4-trlazo1es ot the formula Melting C.) or boiling point 0.] Empirical mm.) formula 1 One convenient method of preparation is by the transamination of In all cases these products are water insoluble solids and are isolated by filtration, centrifuging or other methods known in the art for insoluble products. Based on a reaction of dithiocarbamates as known from the literature, such as Belgian Patent 706,936 (based on 5 diformylhydrazine with an aliphatic, aromatic or het- U.S. Ser. No. 598,599, filed Dec. 2, 1966), it would be predicted that the product obtained from the above reaction would be an onium metal ethylenebisdithiocarbamate.

The 4-substitutedl ,2,4-triazolemetal salt complexes 10 are solids with characteristic melting or decomposition points. In many instances they may be recrystallized from appropriate solvents such as water, dimethylformamide, acetone and mixutures of these.

Certain of the intermediate 4-substitutedtriazoles are known compounds.

N,N-dimethylformamide azine with primary amines, as described by Bartlett and Humphrey, J. Chem. Soc. 1967, 1664-1666. The reaction may be depicted as MezNCH=N-N=CHNMe RNHz The reaction is conveniently run at reflux temperature Prep.

S C 00 8 .6 9788716786337365m. 1 98 mflm35379 m wwnm m m mmmeaaseah mhazaza 2 32. s .33.. oomp mmmmo mNN 5m was mfimmmmmfimm a. mH mm 000000000000 0 00000 omo mc wnwmmmmmmm "m u m m W m m mm m m m mm." mm 03 a r a .3 1 1 m. as. m W

11.0% and 17.3% 8, calculated for CoHIaNOS is I TABLE 140mm ksubstituted-IJA-triazoles oi the formula l ll L N Melting C.) or Analytical data I boilingpoint C./ Empirical Prep. R m.) formula Percent 0 Percent H Percent N is 2,4-o1lotm0oi1.o1a,..-- 115-111 .i oio asonmo 46.6 (46.5) 3.1 (3.5 1&3 (16.3) AS 4-ClCeH4OCH2CHz 7475 CioHrnClNaO 50.8 (53.8) 4.4 (4. 5) 20-9 (18.9) 4-(JlCuH4SOHzCHz 73-75". CmHioClNsS I 49.9 (50.3) 4.2 (4. 2) 14.7 (14. 7) 4-CHaOCgH4SCH2CHg 74-76 CUHHN OS 56.2 (56.2) 5.7 (5. 5) 18.1 (17.9) 3,4-CliCaH SCH2CHz 8 127-129 CniHoClzNsS 53.8 (43.7) 3.5 (3. 3) 15.1 (15.3)

8 Figures in parentheses are those calculated from the empirical formula. b The intermediate Aryl-SCHKJHMH: was made byreaction ot2-chioroethylamlne hydrochloride with the appropriate sodium thiophenate.

a 4-ClCiH4SCH2CHzNHz distilled at 97-l00 C./.1 mm. and was found by analysis to contain 512% O, 5.5% H, 19.1% Cl, 7.82% N and 16.2% S; calculated for CKHIOCINS is 41.1% 06 5.471, H, 18.9% CI, 7.5% N and 17.1% S.

d 4'CHZOCUH4SCH2CHZNH2 distilled at 110-151 076 3.4-ClzCiHaSCH2CH2NH2 distilled at 160-161 6.2% N and 14.3% S; calculated for CsHoClzNS is 43.3 C

The following are typical examples of preparations of 4-substitutcd-l,2,4-triazole-metal salt complexes.

EXAMPLE 4 Preparation of 4-butyl-l ,2,4-triazole-nickel nitrate complex i a. Preparation of 4-butyl-l,2,4triazole I A 2-liter flask was charged with 440 g. (3 moles) of triethyl orthoformate, 120 g. (2 moles) of formylhydrazine and 800 ml. of anhydrous methanol. The reaction mixture was stirred at reflux temperature (65-70 C.) for 3.5 hrs. The progress of the reaction was followed hourly by means of gas-liquid chromatography. The reaction mixture was cooled to 60 C. and 146 g. (2 moles) of n-butylaminc was added in minutes. A slight exothermraised the temperature about 5 C. The reaction mixture was stirred at reflux temperature for 3 hours and was then stripped of solvent and excess triethyl orthoformate by heating on a steam bath at reduced pressure, down to mm. There was obtained a yellow oil residue of 250 g. which by elution gasliquid chromatography was shown to be at least 85 percent of 4-butyl-l ,2,4-triazole. A further stripping of this residue at a pot temperature of 190 C. and 10 mm. pressure gave 216 g. of light amber oil residue which was an 86 percent yield of crude 4-butyl-l ,2,4-triazole, shown to be 93 percent pure by gas-liquid chromatography. The product was further purified by distillation. The main fraction distilled at l85 C. at 2 mm. pressure and was a 77 percent weight yield of 4-n-butyl-l,2,4- triazole melting at 50 C.

b. Preparation of 4-butyl-l ,2,4-triazole-nickel nitrate complex An aqueous solution of l.l6 g. (0.004 mole) of nickel nitrate in 10 ml. of water was added to an aqueous solution of l g. (0.008 mole) of .4-butyl'l,2,4- triazole in 10 ml. of watertA precipitate resulted and was filtered off, washed with water and dried to give 1.2 g. of 4-butyl-l ,2,4-triazole-nickel nitrate complex melting at 250 C. in which the mole ratio of triazole to NI(NO3)2 was 2:]- I

When an equivalent quantity of nickel chloride was substituted for nickel nitrate in the above, a blue solution resulted. The 4-butyl'1,2,4-triazole-nickel chloride ./.01 mm. and was found by analysis to contain 57.7% C, 6.9% H, 7.3% N,

0 C. 7.1% H, 7.7% N, 8.7% O and 17.5% S.

C./.05 mm. and was found by analysis to contain 43.0% C, 4.6% H, 32. 0% 01,

4.0% H, 32.0% C]. 6.3% N and 14.4% 5.

EXAMPLE 9 .Preparation of 4-bu tyl-l,2,4-triazole silver" nitrate complex. t a

An aqueous solution of 1.36 g. (0.008 mole) of silver nitrate in 10 ml. of water was added to an aqueous solution of l g. (0.008 mole) of 4-butyl-l,2,4-triazole in 10 ml. of water. A precipitate formed and was filtered off, washed with water and dried to give 1.6 g. of 4-butyll,2,4-triazole-silver nitrate complex melting at 209-2ll C. in which the mole ratio of triazole to AgNO was i: 1. When twice the amount-of triazole was employed no precipitate formed.

complex in which the mole ratio of triazole to NiCl EXAMPLE 10 melting at l05-l07 C. in which the mole ratio of triazole to HgCl was 1:1. The same product was formed when twice as much 4-butyl-l,2,4-triazole was employed.

EXAMPLE 1 l Preparation of 4-butyl-l ,2,4-triazole-zinc ethylenebisdithiocarbamate complex To a solution of 56.3 g. (0.2 mole) of 91 percent disodium ethylenebisdithiocarbamate in 177 g. of deionized water in a beaker was added 25 g. (0.2 mole) of 4-butyl-l,2,4-triazole. To the resulting solution was added over a period of 29 minutes a solution of 27.3 g. (0.2 mole) of zinc chloride in 27.3 g. of water. A slight exotherm raised the temperature from 26 to 31 C. and a thick white slurry resulted. After stirring for 1 hr. the product was filtered giving 229 g. of filtrate having a pH of about 8 and a wet cake. The solid residue was washed with 500 ml. of deionized water and dried to constant weight to give 76 g. of white solid melting with decomposition at 122 to l24 C. The product is a complex containing equimolar ratios of 4-butyl-l ,2,4- triazole, zinc ion and ethylenebisdithiocarbamate.

Preparation of 4-benzyl-l,2,4-triazole-zinc chloride complex.

An ethanolic solution of 0.428 g. (0.00314 mole) of The compounds of this invention are fungicides and are particularly useful for the control of wheat leaf rust, Puccinia recondita and in some instances for the control of damping-off diseases. Compounds of the type of zinc chloride in 20 ml. of ethanol was added to an etha- 53 7 have bmad spectrlm nolic solution of l g. (0.00628 mole) of 4-benzyl-l,2,4- 1 9 4 b d 4 triazole in 25 ml. of ethanol. A precipitate formed and F e l' f smute 1121 'mazoles of was filtered oil, washed with ethanol and dried to give ormlga are a P tjunglcldeshfor lfigl 12 cereal 1.2 g. of 4-ben yl-l,2,4-triazole-zinc chloride complex l O l g fi l l g is T l p ytotox' melting at 238-242 C. in which the mole ratio of tril l e o owmg a F g'ves t e average in ury 1n a standard preliminary postemergence herbiazole to ZnCl was 2.1. l l lb f I In Tables ll and Ill are listed typical examples of the a f 3a I I g acre tylnca l' novel compounds of this invention with physical charg M a e "a 1 51 1 g D acteristics and analyses. -2--. onous onocots) an typica icotye onous 1- cots) plants were sprayed with the test chemical two weeks after planting and the average percent injury was observed 2 weeks later.

Table IV TABLE II Nw aw Compounds 0mm structure Hel'blcldfil Activity 61 4-Substituted-l,-2.4:-triazoles Average in ury N--N Preparation Monocots Dicots l i A 1) L (ML) B 2 20 5 C 12 WW R a. 2 I 1) 1s 22 E 5 50 F 0 35 1-1 0 58 Melting I I5 58 1111 J 22 Ex. R a M X n (300.) 30 K 75 92 2 011 2 210-220 g3 2g 2 1 11 5 145-153 N o 5 2 N1++ 25 2 Ni 2 250 O 35 11 8 2 2:1 1 269-271 g 8 g 2 zn++ 2 123-125 3 5 s 45 68 1 A 1 209-211 1 tip- 2 -107 T 38 72 1 zn++ 1 1 122-124 U 52 55 1 (311 1 -120 v 40 35 1 Mn 1 195-200 w 5 52 1 N1++ (CHNHCSS 1 194-198 X 38 46 1 cd++ (CH1NHCSS). 1 250-200 Y 0 65 1 FBH (-OHzNHCSS;:.--. 1 140150 1 811* (-CH1NHCSS- 1-... 1 125127 40 Z 35 22 18.... Iso-CiH1|. 2 zn++ o1 2 157-158 AA 22 35 19.--. 7'Z-C3H11-.-.. 2 zn++ c1-.. 2 -144 AB 32 30 20 C(H5CH2... 2 Zl'l Cl.-. 2 238-242 AC 2 0 21.... 0.115. 2 Zn: c1 2 228-228 AD 18 22-... 2-pyr1dyl.- 2 Zn 0) 2 192-193 AB 38 95 l Decomposition. AF 42 2 Made with either the chloride or sulfate salt. 45 AG. 8 80 Table III Analytical Data on l-Substituted-l,2,4-triazole Metal Salt Complexes Example Empirical Formula C H N Other 1 C l-l N cncl 35.1 (37.6) 5.8 (5.7) 20.6 21.9) Cu. 14.3 16.5 H2O 6.5 (none) 2 c 11,,r-1,-191=eC1 38.1 38.2) 6.1 5.8 22.1 22.3) Fe, 12.0 14.9) 3 C H N -%NiCl, 33.9 37.9 5.8 (5.8 22.1 (20.8) Ni, 14.6 (15.5) 4 C l-l N -%Ni(NO 33.3 (35.8) 5.1 (5.9) 25.8 (25.9) Ni. 25.8 25.9) 5 (3.11,,81 -96znc1 37.5 (37.3) 5.4 (5.7) 20.1 21.7 Zn, 18.2 18.3) 6 C..11, 1-1,-14Zn No 35.9 (32.7) 5.1 5.1) 25.3 25.4 Zn, 11.1 14.8 7 C l-l N ZnSo 34.3 (35.0) 5.5 5.4) 20.2 20.4) 211, 14.7 15.8 8 C.1-1,,1-1,-1ezn(C 11 0, 44.3 (44.3) 6.5 (6.5) 19.6 (19.4) Zn. 15.2 (15.1) 9 c..1-1.,r-1,-A 1-1o 24.6 24.4 3.9 (3.7) 19.3 19.0 Ag, 35.0 (36.6) 10 C,H,,N;-HgCl 18.2 18.2 2.8 (2.8 10.5 (10.6 Hg. 36.9 (50.5) 11 c u N -zncnnms. 28.0 (30.0) 4.1 4.3) 16.4 (17.5) Zn. 15.9 (16.3) 12 C.,11 N,-cuc.1-1,1-1,s 25.2 (30.1) 3.4 (4.3) 15.2 (17.5) Cu, 12.9 (15.9) 13 0.,1-1,,N,-MnC.11,r-1,s 30.0 (30.7 4.7 (4.4) 17.8 (17.9 Mn, 11.7 (14.1) 14 c l-l N -NiqmN s. 30.5 30.9) 4.4 (4.3) 17.8 (17.8 Ni, 13.8 14.9) 15 C,H,,N,-CdC.H.N,s. 24.9 (26.8 3.7 (3.8) 15.1 (15.6) Cd. 25.4 (25.1) 16 123,11,,N,-1=6C.11..N,s 33.1 30.7) 5.0 (4.4) 20.1 (17.9) Fe. 14.4 (14.3) 17 C fl N 'snQmN- s 23.8 (26.4) 3.4 (3.8) 13.7 (15.4) sn, 22.2 (26.1) 18 cm N nzi-icl, 38.2 (40.6) 6.0 (6.3 19.2 (20.3) Zn, 17.5 (15.7) l9 C H|QN3'%Z"CI2 48.9 (48.l) 8.1 (7.7) l7.3 (16.9) Zn. l5.l (|3.l) 20 C,,|-1,,1-1 19.ZnC1 47.4 (47.6) 4.1 4.0) 18.1 (18.5) Zn, 14.7 (14.3) 21 C,,H,N;,%ZnCl 44.8 45.1) 3.3 (3.3) 19.9 (19.7) Zn. 15.6 (15.3 22 C H N 'l2ZnCl, 39.6 (39.3) 2.9 (2.8) 26.2 (26.2) Zn. 16.0 (15.2

a Figures in parentheses are those calculated from the empirical formula Table lVContinued Herbicidal Activity of 4 Substiluted-l,'2.4-tria2oles Average Injury The phytotoxicity of certain of the 4-substituted -l, 2,4-triazoles is particularly manifested when they are employed as a systemic rust fungicide by seed treatment. it has been found that the novel 4-substitutedl ,2,4-triazole-metal salt complexes of this invention are much safer to use, particularly as when applied by the seed treatment method. The following type experiment was run to illustrate this. Wheat seeds (Pennoll variety) were treated with the test compounds at rates of 1,2 and 4 ounces per 100 pounds of seed. The treated seeds were planted in wet non-sterile soil and held at 75 F. One week after planting, the injury tothe germinating seed was observed by stand comparisons.

The percent control of wheat leaf rust, Puccinia recondita, was measured for the same treated seed. In this test, wheat seedlings were inoculated with the leaf rust organism seven days after planting and one week thereafter the percent control of the disease was determined. Table V gives the results of the above tests in comparison with 4-butyl-l,2,4-triazole (Preparation C). Injury ratings are included for the treatments involving 4 ounces per 100 pounds of seed of the test compounds.

Table V a II see Tables l and II b I ounces per I lbs. of seed e w a severe 4+ 3 moderate a slight it will be seen that conversion of a 4-substituted-1,2,4- triazole to a metal salt complex reduces the phytotoxic properties without impairing the fungicidal activity versus leaf rust. H

- agricultural fungicides, the 4-substituted-l,2,4-

triazole-metal salt complexes of this invention may be applied to various loci such as the seed, the soil or'the foliage. For such purposes these compounds may be used in the technical or pure form as prepared, as solutions or as formulations. The compounds are usually taken up in a carrier or are formulated so as to render them suitable for subsequent dissemination as pesticides. For example, the 4-substiituted-l ,2,4 triazolemetal salt complexes may be fomiulated as wettable powders, emulsifiable concentrates, dusts, granular for mulations, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and,when desired, suitable surfactants are incorporated.

It is usually desirable, particularly in the case of foliar spray formulations, to include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives and the like in accordance with agricultural practices. Such adjuvants commonly used in the art may be found in the John W. McCutcheon, lnc. publication Detergents and Emulsifiers 1968 Annual."

in case the 4-substituted 1,2,4l-triazole-metal salt complex is water-soluble, it may be dissolved directly in water to provide an aqueous solution for application. Similarly, the compounds of this invention may be dissolved in a water-miscible liquid, such as methanol, ethanol, isopropanol, acetone, dimeth'ylformamide or dimethyl sulfoxide or mixtures of these with water and such solutions extended with water. The concentration of the solution may vary from 2 percent to 98 percent with a preferred range being 25 percent to percent.

For the preparation of emulsifiable concentrates, the

compound may be dissolved in organic solvents, such as xylene, pine oil, orthodichlorobenzene, methyl oleate, or a mixture of solvents, together with an emulsifying agent which permits dispersion. of thepesticide in water. The concentration of the active ingredient in emulsifiable concentrates is usually 10 percent to 25 percent and, in. flowable emulsion concentrates, this may be as high as 75 percent.

Wettable powders suitable for spraying may be prepared by. admixing the compound with a finely divided solid, such as clays, inorganic silicates and carbonates, and silicas, and incorporating wetting agents, sticking agents, and/or dispersing agents in such mixtures. The concentration of active ingredients in such formulations is usually in the range of 20 percent to 98 percent, preferably 40 percent to 75 percent.

Dusts are prepared by mixing the 4-substituted-l ,2,4- triazole-metal salt complex with finely divided inert solids which may be organic or inorganic in nature. Materials useful for this purpose include botanical flours, silicas, silicates, carbonates and clays. One convenient method of preparing a dust is to dilute a wettable powder with a finely divided carrier. Dust concentrates containing 20 percent to percent of the active ingredient are commonly made and are subsequently diluted to 1 percent to 10 percent use concentration.

The 4-substituted-l,2,4-triazole-metal salt complex can be applied as fungicidal sprays bythe methods commonly employed, such as conventional highgallonage hydraulicsprays, low gallonage sprays, airblast spray, aerial sprays and dusts. The dilution and rate of application will depend upon the type of equipment the-method of application and the disease to be controlled, but the amount is usually 0.1 lb. to 25 lbs. per acre of the active ingredient.

As a seed protectant, the amount of toxicant coated on the seed is usually at a dosage rate of about 0.1 to ounces per hundred pounds of seed. As a soil fungicide the chemical may be incorporated in the soil or applied to the surface usually at a rate of0.l to lbs. per acre. As a foliar fungicide the toxicant is usually applied to growing plants at a rate of 0.25 to 10 pounds per acre.

The compounds of this invention may be used as the sole biocidal agents alone or in admixture,'or they may be employed with other pesticides, such as other fungicides, insecticides, miticides and bird repellents.

Other fungicides which maybe combined with the compounds of this invention include dithiocarbamates and derivatives such as ferric dimethyldithiocarbamates (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebis-dithiocarbamate (maneb) and its coordination product with zinc ion, zinc ethylenebisdithiocarbamate (zineb), tetramethylthiuram disulfide (thiram) and 3,5-dimethyl-l,3,5-2H- tetrahydrothiadiazine-Z-thione; nitrophenol derivatives such as dinitro-( l-methylheptyl)-phenyl crotonate (dinocap), 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate (binapacryl) and 2-sec-butyl-4,6- dinitrophenyl isopropyl carbonate; heterocyclic structures such as N-trichloro methylthio-tetrahydrophthalimide (captan), N-trichloromethylthiophthalimide (folpet), 2-heptadecyl-2-imidazoline glyodin 2,4-dichloro-6-(o-chloro-anilino)-s-triazine, diethyl phthalimidophosphorothioate, S-amino-l- [bis(dimethylamino)phosphinyl ]-3-phenyll ,2,4- triazole, 5 etho y Qa -trichloromethyl-l ,2,4-thiadiazole,

2,3-dicyano-l ,4-dithiaanthraquinone (dithianon 2- thio-l ,3-dithio-[4,5-b]quinoxaline (thioquinox), l-

(butylcarbamoyl )-2-benzimidazole carbamic acid methyl ester (benomyl), 4-( 2- chlorophenylhydrazone )-3-methyl-5 -i,soxazolone,

pyridine-2-thioll -oxide, 8-hydroxyquinoline, 2,3-

dihydro-S -carboxanilido-6-methyll ,4-oxathiin-4,4- dioxide, and his (p-chlorophenyl)-3 pyridinemethanol; and miscellaneous fungicides such as dodecylguanidine acetate (dodine), 3-[2-(3,5-dimethyl-2- oxycyclohexyl)-2-h ydroxyethyl]glutarimide (cycloheximde), phenylmercuric acetate, N-ethylmercuril,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercuric monoethanolammonium lactate, 2,3-dichloro-l,4-napthoquinone, 1,4- dichloro-2,S-dimethoxybenzene, p-dimethylaminobenzenediazo sodium sulfonate, Z-chloro-lnitropropane, polychloronitrobenzenes such as pentachloronitrobenzene, methyl isothiocyanate, fungicidal antibiotics such as griseofulvin or kasugamycin, tetrafluorodichloroacetone, l -phenylthiosemicarbazide, Bordeaux mixture, nickel-containing compounds and sulfur.

We claim:

1. A method of protecting plants against phytopathogenic fungi which comprises applying to the seed of the plant to be protected prior to the planting of said seed, 2 oz. per lbs. of seed of 4-butyl-l ,2,4-triazolenickel chloride complex.

2. A method of protecting plants against phytopathogenic fungi which comprises applying to the seed of the plant to be protected prior to the planting of said seed, 1 oz. per 100 lbs. of seed of 4-butyl-i ,2,4-triazolenickel chloride complex.

i =8 4' t II UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,821,376 Dated June 28, 197% Horst O. Bayer, Richard St, Cook, and William Co vonMeye It is certified that error appears in the above-identified! patent and that said Letters Patentare hereby corrected as shown below:

In the title, "nickel" should be metal-"o In Table I, under R, Preparation F entry "n-C -H should be t-C -H In Table I, I under %N, Preparation L. entry "20O(20.,2)" should be --2ono(2o1)-- Signal and Scalcd this Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks 

2. A method of protecting plants against phytopathogenic fungi which comprises applying to the seed of the plant to be protected prior to the planting of said seed, 1 oz. per 100 lbs. of seed of 4-butyl-1,2,4-triazole-nickel chloride complex. 